Division of Surface and Corrosion Science, School of Chemical Science and Engineering, Royal Institute of Technology (KTH), Drottning Kristinas väg 51, SE-100 44 Stockholm, Sweden.
Integr Environ Assess Manag. 2010 Jul;6(3):456-68. doi: 10.1002/ieam.66.
Ferrochromium alloys are manufactured in large quantities and placed on the global market for use as master alloys (secondary raw materials), primarily for stainless steel production. Any potential human exposure to ferrochromium alloy particles is related to occupational activities during production and use, with 2 main exposure routes, dermal contact and inhalation and subsequent digestion. Alloy and reference particles exposed in vitro in synthetic biological fluids relevant for these main exposure routes have been investigated in a large research effort combining bioaccessibility; chemical speciation; and material, surface, and particle characteristics. In this paper, data for the dermal exposure route, including skin and eye contact, will be presented and discussed. Bioaccessibility data have been generated for particles of a ferrochromium alloy, stainless steel grade AISI 316L, pure Fe, pure Cr, iron(II,III)oxide, and chromium(III)oxide, upon immersion in artificial sweat (pH 6.5) and artificial tear (pH 8.0) fluids for various time periods. Measured released amounts of Fe, Cr, and Ni are presented in terms of average Fe and Cr release rates and amounts released per amount of particles loaded. The results are discussed in relation to bulk and surface composition of the particles. Additional information, essential to assess the bioavailability of Cr released, was generated by determining its chemical speciation and by providing information on its complexation and oxidation states in both media investigated. The effect of differences in experimental temperature, 30 degrees C and 37 degrees C, on the extent of metal release in artificial sweat is demonstrated. Iron was the preferentially released element in all test media and for all time periods and iron-containing particles investigated. The extent of metal release was highly pH dependent and was also dependent on the medium composition. Released amounts of Cr and Fe were very low (close to the limit of detection, <0.008% of particles released or dissolved as iron or chromium) for the alloy particles (ferrochromium alloy and stainless steel), the pure Cr particles, and the metal oxide particles. The released fraction of Cr (Cr/[Cr + Fe]) varied with the material investigated, the test medium, and the exposure time and cannot be predicted from either the bulk or the surface composition. Chromium was released as noncomplexed Cr(III) and in addition in very low concentrations (<3 microg/L). Nickel released was under the limit of detection (0.5 microg/L), except for ultrafine stainless steel particles (<10 microg/L). It is evident that media chemistry and material properties from a bulk and surface perspective, as well as other particle characteristics, and the chemical speciation of released metals have to be considered when assessing any potential hazard or risk induced by sparingly soluble metal or alloy particles.
铬铁合金的产量很大,被投放全球市场作为母合金(二次原料)使用,主要用于生产不锈钢。人类可能接触到铬铁合金颗粒与生产和使用过程中的职业活动有关,接触途径主要有两种,即皮肤接触和吸入以及随后的消化。体外研究已经针对在与这两种主要暴露途径相关的合成生物流体中暴露的合金和参考颗粒进行了大量研究,结合生物利用度、化学形态、材料、表面和颗粒特性。本文将介绍并讨论与皮肤暴露途径(包括皮肤和眼睛接触)有关的数据。已经在人工汗液(pH 值 6.5)和人工泪液(pH 值 8.0)中对铬铁合金、不锈钢等级 AISI 316L、纯铁、纯铬、铁(II,III)氧化物和氧化铬颗粒进行了一段时间的浸泡,生成了生物利用度数据。以单位颗粒负载量下的平均铁和铬释放率和释放量来表示测量得到的 Fe、Cr 和 Ni 释放量。研究结果与颗粒的体相和表面组成有关。通过确定化学形态以及提供两种介质中铬的络合和氧化态信息,提供了评估释放的 Cr 生物有效性的必要信息。实验温度 30°C 和 37°C 对人工汗中金属释放程度的影响也得到了证明。在所有测试介质和所有时间段内,铁都是所有被测试颗粒中优先释放的元素。金属释放程度高度依赖于 pH 值,也依赖于介质组成。对于合金颗粒(铬铁合金和不锈钢)、纯 Cr 颗粒和金属氧化物颗粒,Cr 和 Fe 的释放量非常低(接近检测限,<0.008%的颗粒释放或溶解为铁或铬)。Cr 的释放分数(Cr/[Cr + Fe])因所研究的材料、测试介质和暴露时间而异,不能根据体相或表面组成进行预测。铬以非络合 Cr(III)的形式释放,此外,浓度非常低(<3μg/L)。除了超细不锈钢颗粒(<10μg/L)外,释放的镍都低于检测限(0.5μg/L)。显然,在评估由难溶性金属或合金颗粒引起的任何潜在危害或风险时,必须考虑介质化学性质和体相及表面特性以及其他颗粒特性和释放金属的化学形态。